Improving the scientific reliability of biological detection of explosives by Canis familiaris: Active odour signatures and their implications

The use of canines as a method of detection of explosives is well established worldwide and those applying this technology range from police forces and law enforcement to humanitarian agencies in the developing world. Despite the recent surge in publication of novel instrumental sensors for explosives detection, canines are still regarded by many to be the most effective real-time field method of explosives detection. However, unlike instrumental methods, currently it is difficult to determine detection levels, perform calibration of the canines' ability or produce scientifically valid quality control checks. Accordingly, amongst increasingly strict requirements regarding forensic evidence admission such as Frye and Daubert, there is a need for better scientific understanding of the process of canine detection. ^ When translated to the field of canine detection, just like any instrumental technique, peer reviewed publication of the reliability, success and error rates, is required for admissibility. Commonly training is focussed towards high explosives such as TNT and Composition 4, and the low explosives such as Black and Smokeless Powders are added often only for completeness. ^ Headspace analyses of explosive samples, performed by Solid Phase Microextraction (SPME) paired with Gas Chromatography - Mass Spectrometry (GC-MS), and Gas Chromatography - Electron Capture Detection (GC-ECD) was conducted, highlighting common odour chemicals. The odour chemicals detected were then presented to previously trained and certified explosives detection canines, and the activity/inactivity of the odour determined through field trials and experiments. ^ It was demonstrated that TNT and cast explosives share a common odour signature, and the same may be said for plasticized explosives such as Composition C-4 and Deta Sheet. Conversely, smokeless powders were demonstrated not to share common odours. An evaluation of the effectiveness of commercially available pseudo aids reported limited success. The implications of the explosive odour studies upon canine training then led to the development of novel inert training aids based upon the active odours determined. ^

A framework for automatic feature extraction from airborne light detection and ranging data

Recent advances in airborne Light Detection and Ranging (LIDAR) technology allow rapid and inexpensive measurements of topography over large areas. Airborne LIDAR systems usually return a 3-dimensional cloud of point measurements from reflective objects scanned by the laser beneath the flight path. This technology is becoming a primary method for extracting information of different kinds of geometrical objects, such as high-resolution digital terrain models (DTMs), buildings and trees, etc. In the past decade, LIDAR gets more and more interest from researchers in the field of remote sensing and GIS. Compared to the traditional data sources, such as aerial photography and satellite images, LIDAR measurements are not influenced by sun shadow and relief displacement. However, voluminous data pose a new challenge for automated extraction the geometrical information from LIDAR measurements because many raster image processing techniques cannot be directly applied to irregularly spaced LIDAR points. ^ In this dissertation, a framework is proposed to filter out information about different kinds of geometrical objects, such as terrain and buildings from LIDAR automatically. They are essential to numerous applications such as flood modeling, landslide prediction and hurricane animation. The framework consists of several intuitive algorithms. Firstly, a progressive morphological filter was developed to detect non-ground LIDAR measurements. By gradually increasing the window size and elevation difference threshold of the filter, the measurements of vehicles, vegetation, and buildings are removed, while ground data are preserved. Then, building measurements are identified from no-ground measurements using a region growing algorithm based on the plane-fitting technique. Raw footprints for segmented building measurements are derived by connecting boundary points and are further simplified and adjusted by several proposed operations to remove noise, which is caused by irregularly spaced LIDAR measurements. To reconstruct 3D building models, the raw 2D topology of each building is first extracted and then further adjusted. Since the adjusting operations for simple building models do not work well on 2D topology, 2D snake algorithm is proposed to adjust 2D topology. The 2D snake algorithm consists of newly defined energy functions for topology adjusting and a linear algorithm to find the minimal energy value of 2D snake problems. Data sets from urbanized areas including large institutional, commercial, and small residential buildings were employed to test the proposed framework. The results demonstrated that the proposed framework achieves a very good performance. ^

Improved sampling, pre-concentration, and detection of hidden explosives and illicit drugs by a novel solid phase microextraction geometry coupled to ion mobility spectrometry

The 9/11 Act mandates the inspection of 100% of cargo shipments entering the U.S. by 2012 and 100% inspection of air cargo by March 2010. So far, only 5% of inbound shipping containers are inspected thoroughly while air cargo inspections have fared better at 50%. Government officials have admitted that these milestones cannot be met since the appropriate technology does not exist. This research presents a novel planar solid phase microextraction (PSPME) device with enhanced surface area and capacity for collection of the volatile chemical signatures in air that are emitted from illicit compounds for direct introduction into ion mobility spectrometers (IMS) for detection. These IMS detectors are widely used to detect particles of illicit substances and do not have to be adapted specifically to this technology. For static extractions, PDMS and sol-gel PDMS PSPME devices provide significant increases in sensitivity over conventional fiber SPME. Results show a 50–400 times increase in mass detected of piperonal and a 2–4 times increase for TNT. In a blind study of 6 cases suspected to contain varying amounts of MDMA, PSPME-IMS correctly detected 5 positive cases with no false positives or negatives. One of these cases had minimal amounts of MDMA resulting in a false negative response for fiber SPME-IMS. A La (dihed) phase chemistry has shown an increase in the extraction efficiency of TNT and 2,4-DNT and enhanced retention over time. An alternative PSPME device was also developed for the rapid (seconds) dynamic sampling and preconcentration of large volumes of air for direct thermal desorption into an IMS. This device affords high extraction efficiencies due to strong retention properties under ambient conditions resulting in ppt detection limits when 3.5 L of air are sampled over the course of 10 seconds. Dynamic PSPME was used to sample the headspace over the following: MDMA tablets (12–40 ng detected of piperonal), high explosives (Pentolite) (0.6 ng detected of TNT), and several smokeless powders (26–35 ng of 2,4-DNT and 11–74 ng DPA detected). PSPME-IMS technology is flexible to end-user needs, is low-cost, rapid, sensitive, easy to use, easy to implement, and effective. ^

Field programmable gate array based target detection and gesture recognition

The move from Standard Definition (SD) to High Definition (HD) represents a six times increases in data, which needs to be processed. With expanding resolutions and evolving compression, there is a need for high performance with flexible architectures to allow for quick upgrade ability. The technology advances in image display resolutions, advanced compression techniques, and video intelligence. Software implementation of these systems can attain accuracy with tradeoffs among processing performance (to achieve specified frame rates, working on large image data sets), power and cost constraints. There is a need for new architectures to be in pace with the fast innovations in video and imaging. It contains dedicated hardware implementation of the pixel and frame rate processes on Field Programmable Gate Array (FPGA) to achieve the real-time performance. ^ The following outlines the contributions of the dissertation. (1) We develop a target detection system by applying a novel running average mean threshold (RAMT) approach to globalize the threshold required for background subtraction. This approach adapts the threshold automatically to different environments (indoor and outdoor) and different targets (humans and vehicles). For low power consumption and better performance, we design the complete system on FPGA. (2) We introduce a safe distance factor and develop an algorithm for occlusion occurrence detection during target tracking. A novel mean-threshold is calculated by motion-position analysis. (3) A new strategy for gesture recognition is developed using Combinational Neural Networks (CNN) based on a tree structure. Analysis of the method is done on American Sign Language (ASL) gestures. We introduce novel point of interests approach to reduce the feature vector size and gradient threshold approach for accurate classification. (4) We design a gesture recognition system using a hardware/ software co-simulation neural network for high speed and low memory storage requirements provided by the FPGA. We develop an innovative maximum distant algorithm which uses only 0.39% of the image as the feature vector to train and test the system design. Database set gestures involved in different applications may vary. Therefore, it is highly essential to keep the feature vector as low as possible while maintaining the same accuracy and performance^

Automating Hospitality Information: Network Technology and Systems Management

The local area network (LAN) interconnecting computer systems and soft- ware can make a significant contribution to the hospitality industry. The author discusses the advantages and disadvantages of such systems.

Evaluation of non-contact sampling and detection of explosives using receiver operating characteristic curves

The growing need for fast sampling of explosives in high throughput areas has increased the demand for improved technology for the trace detection of illicit compounds. Detection of the volatiles associated with the presence of the illicit compounds offer a different approach for sensitive trace detection of these compounds without increasing the false positive alarm rate. This study evaluated the performance of non-contact sampling and detection systems using statistical analysis through the construction of Receiver Operating Characteristic (ROC) curves in real-world scenarios for the detection of volatiles in the headspace of smokeless powder, used as the model system for generalizing explosives detection. A novel sorbent coated disk coined planar solid phase microextraction (PSPME) was previously used for rapid, non-contact sampling of the headspace containers. The limits of detection for the PSPME coupled to IMS detection was determined to be 0.5-24 ng for vapor sampling of volatile chemical compounds associated with illicit compounds and demonstrated an extraction efficiency of three times greater than other commercially available substrates, retaining >50% of the analyte after 30 minutes sampling of an analyte spike in comparison to a non-detect for the unmodified filters. Both static and dynamic PSPME sampling was used coupled with two ion mobility spectrometer (IMS) detection systems in which 10-500 mg quantities of smokeless powders were detected within 5-10 minutes of static sampling and 1 minute of dynamic sampling time in 1-45 L closed systems, resulting in faster sampling and analysis times in comparison to conventional solid phase microextraction-gas chromatography-mass spectrometry (SPME-GC-MS) analysis. Similar real-world scenarios were sampled in low and high clutter environments with zero false positive rates. Excellent PSPME-IMS detection of the volatile analytes were visualized from the ROC curves, resulting with areas under the curves (AUC) of 0.85-1.0 and 0.81-1.0 for portable and bench-top IMS systems, respectively. Construction of ROC curves were also developed for SPME-GC-MS resulting with AUC of 0.95-1.0, comparable with PSPME-IMS detection. The PSPME-IMS technique provides less false positive results for non-contact vapor sampling, cutting the cost and providing an effective sampling and detection needed in high-throughput scenarios, resulting in similar performance in comparison to well-established techniques with the added advantage of fast detection in the field.

Waveform Detection of Conspecifics in the Weakly Electric Fish Gymnotus Carapo

Weakly electric fish use electric fields for communication and location of objects. Electroreceptors that are located around the mouth and along the length of the body are used in order to "decode" the electric organ discharge (EOD). The knollenorgan in Mormyriformes aids in distinguishing between different EODs. Gymnotiformes, however, have no such electroreceptors. How then are Gyrnnotiformes distinguishing between conspecific EODs? In this study scan sampling was investigated to determine whether Gymnotus carapo uses this mechanism to differentiate between distinct EODs. After determining whether Gymnotus carapo was discriminating between neighbor and stranger EODs, these same EODs were played to the test fish either jittered (the EOD of the test fish and that of the playback could not coincide) or non-jittered (the two EODs could coincide). The results show that the test fish was not discriminating between neighbor and stranger EODs. Thus, conclusions about the use of scan sampling by Gymnotus carapo to distinguish between EODs cannot be made.

Development of advanced capillary electrophoresis techniques with UV and mass spectrometry detection for forensic, pharmaceutical and environmental applications

Capillary electrophoresis (CE) is a modern analytical technique, which is electrokinetic separation generated by high voltage and taken place inside the small capillaries. In this dissertation, several advanced capillary electrophoresis methods are presented using different approaches of CE and UV and mass spectrometry are utilized as the detection methods. ^ Capillary electrochromatography (CEC), as one of the CE modes, is a recent developed technique which is a hybrid of capillary electrophoresis and high performance liquid chromatography (HPLC). Capillary electrochromatography exhibits advantages of both techniques. In Chapter 2, monolithic capillary column are fabricated using in situ photoinitiation polymerization method. The column was then applied for the separation of six antidepressant compounds. ^ Meanwhile, a simple chiral separation method is developed and presented in Chapter 3. Beta cycodextrin was utilized to achieve the goal of chiral separation. Not only twelve cathinone analytes were separated, but also isomers of several analytes were enantiomerically separated. To better understand the molecular information on the analytes, the TOF-MS system was coupled with the CE. A sheath liquid and a partial filling technique (PFT) were employed to reduce the contamination of MS ionization source. Accurate molecular information was obtained. ^ It is necessary to propose, develop, and optimize new techniques that are suitable for trace-level analysis of samples in forensic, pharmaceutical, and environmental applications. Capillary electrophoresis (CE) was selected for this task, as it requires lower amounts of samples, it simplifies sample preparation, and it has the flexibility to perform separations of neutral and charged molecules as well as enantiomers. ^ Overall, the study demonstrates the versatility of capillary electrophoresis methods in forensic, pharmaceutical, and environmental applications.^

Biohazard neutralization based on lipid technology

A rapid detection and neutralization method for biowarfare agents would be a great biodefense in war times. With this purpose, liposomes were developed following the lipid film formation, rehydration, and extrusion procedure as the production method. MgOCl2 was encapsulated in the liposomes and it was tested with three different bacterium B. cereus; B. thuringiensis; and B. subtilis. For specificity, the liposomes were modified with a polyclonal antibody against B. cereus and B. subtilis. The liposomes were characterized using a Malvern Zetasizer Instrument, and the study revealed stability of the liposomes stored at 4°C for a period of 15 days. A live/dead assay revealed a significant reduction of bacterium incubated with MgOCl2-liposomes. Smaller reduction percentages, but yet significant, were observed with the MgOCl2-immunoliposomes. A colony growth assay revealed a significant reduction percentage for empty liposomes, MgOCl2-liposomes, and MgOCl2-immunoliposomes incubated with B. thuringiensis.

Validation of an Analytical Method for the Identification of SmartWater CSI Forensic Marking Technology

SmartWater is a chemical taggant used as a crime deterrent. The chemical taggant is a colorless liquid that fluoresces yellow under ultra-violet (UV) light and contains distinctive, identifiable and traceable elemental composition. For instance, upon a break and entry scenario, the burglar is sprayed with a solution that has an elemental signature custom-made to a specific location. The residues of this taggant persist on skin and other objects and can be easily recovered for further analysis. The product has been effectively used in Europe as a crime deterrent and has been recently introduced in South Florida. In 2014, Fourt Lauderdale Police Department reported the use of SmartWater products with a reduction in burglaries of 14% [1]. The International Forensic Research Institute (IFRI) at FIU validated the scientific foundation of the methods of recovery and analysis of these chemical tagging systems using LA-ICP-MS. Analytical figures of merit of the method such as precision, accuracy, limits of detection, linearity and selectivity are reported in this study. Moreover, blind samples were analyzed by LA-ICP-MS to compare the chemical signatures to the company’s database and evaluate error rates and the accuracy of the method. This study demonstrated that LA-ICP-MS could be used to effectively detect these traceable taggants to assist law enforcement agencies in the United States with cases involving transfer of these forensic coding systems.

Development of Advanced Capillary Electrophoresis Techniques with UV and Mass Spectrometry Detection for Forensic, Pharmaceutical and Environmental Applications

Capillary electrophoresis (CE) is a modern analytical technique, which is electrokinetic separation generated by high voltage and taken place inside the small capillaries. In this dissertation, several advanced capillary electrophoresis methods are presented using different approaches of CE and UV and mass spectrometry are utilized as the detection methods. Capillary electrochromatography (CEC), as one of the CE modes, is a recent developed technique which is a hybrid of capillary electrophoresis and high performance liquid chromatography (HPLC). Capillary electrochromatography exhibits advantages of both techniques. In Chapter 2, monolithic capillary column are fabricated using in situ photoinitiation polymerization method. The column was then applied for the separation of six antidepressant compounds. Meanwhile, a simple chiral separation method is developed and presented in Chapter 3. Beta cycodextrin was utilized to achieve the goal of chiral separation. Not only twelve cathinone analytes were separated, but also isomers of several analytes were enantiomerically separated. To better understand the molecular information on the analytes, the TOF-MS system was coupled with the CE. A sheath liquid and a partial filling technique (PFT) were employed to reduce the contamination of MS ionization source. Accurate molecular information was obtained. It is necessary to propose, develop, and optimize new techniques that are suitable for trace-level analysis of samples in forensic, pharmaceutical, and environmental applications. Capillary electrophoresis (CE) was selected for this task, as it requires lower amounts of samples, it simplifies sample preparation, and it has the flexibility to perform separations of neutral and charged molecules as well as enantiomers. Overall, the study demonstrates the versatility of capillary electrophoresis methods in forensic, pharmaceutical, and environmental applications.

Fast Detection and Chemical Characterization of Gunshot Residues by CMV-GC-MS and LIBS

Gunshot residue (GSR) is the term used to describe the particles originating from different parts of the firearm and ammunition during the discharge. A fast and practical field tool to detect the presence of GSR can assist law enforcement in the accurate identification of subjects. A novel field sampling device is presented for the first time for the fast detection and quantitation of volatile organic compounds (VOCs). The capillary microextraction of volatiles (CMV) is a headspace sampling technique that provides fast results (< 2 min. sampling time) and is reported as a versatile and high-efficiency sampling tool. The CMV device can be coupled to a Gas Chromatography-Mass Spectrometry (GC-MS) instrument by installation of a thermal separation probe in the injection port of the GC. An analytical method using the CMV device was developed for the detection of 17 compounds commonly found in polluted environments. The acceptability of the CMV as a field sampling method for the detection of VOCs is demonstrated by following the criteria established by the Environmental Protection Agency (EPA) compendium method TO-17. The CMV device was used, for the first time, for the detection of VOCs on swabs from the hands of shooters, and non-shooters and spent cartridges from different types of ammunition (i.e., pistol, rifle, and shotgun). The proposed method consists in the headspace extraction of VOCs in smokeless powders present in the propellant of ammunition. The sensitivity of this method was demonstrated with method detection limits (MDLs) 4-26 ng for diphenylamine (DPA), nitroglycerine (NG), 2,4-dinitrotoluene (2,4-DNT), and ethyl centralite (EC). In addition, a fast method was developed for the detection of the inorganic components (i.e., Ba, Pb, and Sb) characteristic of GSR presence by Laser Induced Breakdown Spectroscopy (LIBS). Advantages of LIBS include fast analysis (~ 12 seconds per sample) and good sensitivity, with expected MDLs in the range of 0.1-20 ng for target elements. Statistical analysis of the results using both techniques was performed to determine any correlation between the variables analyzed. This work demonstrates that the information collected from the analysis of organic components has the potential to improve the detection of GSR.